Monoazo dyestuffs and their metal complex compounds



-R'represents a lower alkyl group,

United States Patent MONOAZO DYESTUFFS AND THEIR METAL COMPLEX COMPOUNDS Willy Steinemann, Basel, and Walter Wehrli, Riehen, lSwitzerland, assignors to Sandoz Ltd., Basel, Switzerand No Drawing. Filed July 14, 1958, Ser. No. 748,184 Claims priority, applicationgSwitzerland July 31, 1957 6 Claims. (Cl. 260151) The present invention relates to monoazo dyestufis and their metal complex compounds which in the metal-free form correspond to the general formula wherein B-z stands for the radical of a coupling component coupled in the ortho-position to z.

v for a substituent capable of taking part in metal complex formation or for one convertible into such a substituent,

z for a phenolic or enolic hydroxy group, or a primary or secondary amino group in ortho-position to the -N=N- group,

n for the number 1 or 2, and

y for the radical of a sulfonic acid amide, an aminosulfonic acid amide, a carboxylic acid amide, a carbamic acid ester or a urea linked through the amino group with alkylene,

and wherein B and the nucleus A may contain further substituents, and to the preparation of such dyestuffs and compounds.

More specifically, the aforesaid metallizable compounds may be characterized by the formula I!) T -(NH-C O-0alkylene-NHu-w),l AN=NB wherein A, B-z, v z, n and y are as precedingly defined, and u stands for -CO or --SO and w stands for amino, lower alkylamino, lower hydroxyalkylamino, lower alkoxyalkylamino, di-(lower alkyl)-amino, lower alkyl, mononuclear aryl, lower alkoxy, lower hydroxy- 'alkoxy or lower alkoxyalkoxy, the alkylene being preferably A series of especially interesting monoazo dyestuffs v and their metal complex compounds correspond in the metal-free state to the formula 1 i represents hydrogen or chlorine,

group or a di-(loweralkyll-amino group,

a mononuclear aryl I or enolic hydroxy group or to a primary or secondary amino group, the monoazo dyestufl formed, which mustcontain at least once in the diazo component or the coupling component or in both the grouping wherein y has the above-named meaning, being subse quently treated with a metal-yielding agent either in substance or on the fiber.

Mixtures of monoazo dyestufls are produced by coupling 1 mol of the diazo compound of an aminobenzene containing in ortho-position to the amino group a substituent which is capable of taking part in metal complex formation or can be converted to fulfill this function with 1 mol or a mixture of two or more coupling-components coupling in the adjacent position .to a phenolic or enolic hydroxy group or to a primary or.secondary amino group; or, alternatively, by coupling 1 mol of a mixture of diazo compounds of two or more aminobenzenes containing in ortho-position to the amino group a substituent capable of metal complex formation -or one convertible into such a substituent either with '1 mol of a coupling component coupling in the adjacent position to a phenolic or enolic hydroxy group or to a primary or secondary amino group 'or with 1 mol of .a mixture of two or more coupling components of the same type. At least one half of the dyestufi molecules of the resultant monoazo dyestuif mixture must contain once in the diazo component or in the coupling component or in both the grouping group; it can also be a halogen atom (chlorine or bro- I mine), which is converted by hydrolysis into a hydroxy group or by condensation with a sulfonic acid amide into a -NH-SO group. be contained in the nucleus A as here defined, thefollowing may be enumerated as examples: halogen atoms (chlorine, bromine), nitrogen, acetylaminoypropionylj amino, benzoylamino, carboxy, 'carbomethoxyamino,

'carbethoxyamino, methyl, ethyl tert. butyl, methoxypsulfonic acid, sulfonic acid amide, sulfonic'acid'methylamide, sulfonic acid dimethylamidefsulfonicacid ('2'- hydroxy) -ethylamide, sulfonic acid di-(2'-hydroxyethyl)- amide, sulfonic acid-(2'- 'or' 3-hydroxy-)-propylamidc, sulfonic acid-(3'-methoxy)-propylauiide, sulfonic acid- (2'-ethoxy ethylamide, sulfonic acid phenylamide, 'sulfonic acid methylphenylacid-(2'-carboxy)-phenylamide, sulfonic acid-N-methyl- N-phenylamide, sulfonic -acid-N-(2'-hydroxy') -ethyl-N- phenyl amide, methylsulfonyl 'groups or a NH-CO- -O- -alkylene'y group.

lowing: hydroxybenzenes, hydroxynaphthailenes,

, Patented Nov. 22, 1960 Of the substituents which may or 'chlorophenylamide, sulfonic The choice of coupling components includes thegfolsulfate. centrated aqueous solution of an alkali metal salt of a naphthalenes, alkylamino-, cycloalkylamino-, aralkylamino-, and arylaminonapththalenes, 1-aryl-3-methyl-5-pyrazolones, acylacetylaminoalkanes, acylacetylarninobenzenes and acylacetylaminonaphthalenes. These coupling components can contain the same substituents as the diazo components, the preferred substituent being the NHCOOalkylene-y group.

Diazotization of the aminobenzenes according to the invention is carried out in the normal manner; the -NH--COO-alkyleney group is stable to acids and lyes at room temperature.

The diazo compounds so formed are coupled with a coupling component containing a p'hen'olic or enolic hydroxy group at to C., preferably in a weakly alkaline or strongly alkaline medium and if desired in presence of pyridine. The coupling reaction with a coupling component containing a primary or secondary amino group is performed at 10 to 20 C. in a Weakly acid, preferably acetic acid, medium. The monoazo compounds formed are precipitated 'from the coupling mass, if necessary by the addition of salt, and filtered off.

Instead of using homogeneous diazo and coupling components, a diazo compound can be coupled with a mixture of two or more coupling components or a mixture of two or more diazo componentswith one, two or more coupling components. The reactants must be so proportioned that at least one half of the dyestutf molecules contain an -NH-COOalkylene-y group. As compared with the homogeneous monoazo dyestuffs, these mixtures of monoazo dyestuffs have the advantage that given the correct choice and proportioning of the individual diazo and coupling components, products are ob tained which possess the best possible properties for every field of use.

The monoazo dyestuffs or monoazo dyestutf mixtures are converted into their metal complex compounds preferably with chromium or cobalt compounds; cobalt compounds, however, are suitable only for those monoazo dyestuffs which contain in ortho-position to the azo group a hydroxy group or a substituent which can be converted into such a group. Metallization is carried out preferably in aqueous solution or in an organic medium, for example in formamide or 2-ethoxyethanol, or in the concentrated aqueous solution of an alkalimetal salt of a low molecular aliphatic monocarboxylic acid. It is advantageous to allow an amount of metal-yielding agent-containing less than two but at least one atom of metal to act upon two molecules of monoazo dyestufi.

Examples of suitable chromium compounds are chromic fluoride, chromic sulfate, chromic'formate, chromicacetate, chromic potassium sulfate or chromic ammonium sulfate. The chromates, e.g. sodium and potassium chromate or bichromate are also eminently suitable for the metallization of the monoazo dyestuffs. The operation is carried out preferably in a strongly caustic alkaline medium to which additions of reducing substances may be made.

Cobalt compounds suitable for the present purpose are e.g. cobaltous formate, cobaltous acetate and cobaltous When metallization is conducted in the conlow molecular aliphatic monocarboxylic acid, water-insoluble metal compounds such as cobalt hydroxide and cobalt carbonate can also be employed.

It is specially advantageous to carry out metallization in an aqueous or alkaline medium, the metal compounds um. They are then filtered ofi, washed it necessary and dried.

The metal-containing azo dyestuffs obtained are metal complex compounds in which essentially one metal atom is combined with two molecules of the monoazo compound. They can be described as 1:2 complexes in which one molecule of the monoazo compound is combined with approximately 0.3 to 0.7 atom of metal.

By simultaneous metallization of two or more monoazo dyestuffs it is possible to arrive at products which, like the monoazo dyestuffs themselves, possesses the best possible properties for every field of application.

The new monoazo dyestuffs and their mixtures dye wool, silk, leather and synthetic polyamide fibers by the one-bath and afterchrome dyeing processes in red, yellow, green, blue, violet, gray, brown and black shades of good fastness to washing, milling, rubbing, potting, acids and alkalis.

The metal-containing azo dyestufis possess surprisingly high solubility in water and show good atfinity for W001, silk, leather and synthetic polyamide fibers from neutral or weakly acid dyebaths, giving red, yellow, green, blue, violet, gray, brown and black shades of good to very good fastness to light, milling, washing, perspiration, carboniza ing, decatizing and pressing. A number of them give a good to very good reserve of cotton, polyacrylonitrile, polyester and acetate fibers upon aftertreatment of the dyeings with hydrosulfite. Dyeings on silk can be almost completely stripped from the fiber by treatment with hydrosulfite. Those dyestufis which are sufficiently soluble in organic solvents are also suitable for dyeing manufactured fibers in the mass prior to spinning and coloring lacquer media and plastics of all types in shades fast to light, washing, perspiration and gas fumes.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 17.8 parts of Z-amino-1-hydroxy-4.6-dichlorobenzene in a mixture of 17 parts of 30% hydrochloric acid and 130 parts of water at 5 are diazotized in the normal way with a solution of 6.9 parts of sodium nitrite in 30 parts of water. Afterwards the diazo suspension is carefully neutralized to a pH value of 5.0 for which purpose. about 29.5 parts of a 17% sodium carbonate solution are required.

The diazo suspension is gradually mixed with a solution, cooled to at least +5 of 34 parts of 7-hydroxynaphthyll-carbamic acid-2-(methylsulfonylamino)-ethyl ester, 8.8 parts of sodium hydroxide, 7 parts of calcined sodium carbonate and 250 parts of water. The mass is stirred at 0-5 until the coupling reaction is completed. The new monoazo dyestutf is salted out, filtered with suction, washed and dried. On grinding it is obtained as a readily soluble powder giving blackish solutions in water and bordeaux-red solutions in concentrated sulfuric acid. The afterchromed dyeings on wool are of blue-gray shade and show excellent fastness to light, washing and milling.

The dyeing method is as follows:

2 parts of the above-described monoazo dyestuff and 10 parts of anhydrous sodium sulfate are dissolved in 6000 parts of water at 40. parts of wool are entered into this dyebath and the temperature increased to 100 in the course of about 30 minutes. 20 parts of 10% acetic acid are added and the bath boiled for 30 minutes; then 20 parts of 10% formic acid are added and the bath boiled for 30 minutes, the evaporated water being gradually replaced; finally 1 part of sodium bichromate in a 10% aqueous solution is added and the bath boiled for a further 30 minutes. The afterchromed Wool dyeing is then removed, rinsed with water and dried. It is dyed in a level blue-gray shade of very good fastness to washing, milling, acids, potting and light.

The new coupling component used for the production of the monoazo .dyestufi of this example can be obtained,

5 .g.' by heating an intimate mixture of 1 mol of 7-hydroxynaphthyl-l-carbaniic acid-2'-chloroethyl ester, 1.1 mols of methanesulfonic acid amide'and 1.2 mols of anhydrous sodium acetate.

EXAMPLE 2 26.4 parts of 2-amino-1-hydroxybenzene-4-sulfonic acid phenylamide in 180 parts of water and 20 parts of concentrated hydrochloric acid are diazotized at 8-12" by the addition of a solution of 6.9 parts of sodium nitrite in 14 parts of water. The diazo suspension, neutralized with sodium carbonate, is run into a cooled solution at 5 of 37 parts of 7-hydroxynaphthyl-l-carbamic acid-2'-(dimethylaminosulfonylamino)-ethyl ester, 8.8 parts of sodium hydroxide, 10 parts of calcined sodium carbonate and 250 parts of water. On completion of coupling the new monoazo dyestuff is isolated in the normal way.

62.8 parts of this dyestufi are dissolved in 400 parts of formamide. The solution is heated to 100-110 and in about 30 minutes 30 parts of crystallized chromic ammonium sulfate are added, the mixture being maintained at 100-120 until formation of the chromium complex is completed. Hereupon'the chroming mass is diluted with 4 to times its volume of water and the chromium corriplex compound saltedout, filtered ofl, dried and ground. The chromium-containing dyestuif is a blue-black powder readily soluble in water; it dyes wool, silk, leather and polyamide fibers in gray shades of very good fastness to light, perspiration, washing and milling.

2 parts of the chromium-containing azo dyestuif thus obtained are dissolved in 4000 parts of water at 40-50. 100 parts of pre-wetted wool are introduced into this dyebath and after the dropwise addition of 2 parts of 100% acetic acid the bath is heated to the boil in 30 minutes and maintained at this temperature for a further 45 minutes. The dyed wool is removed, rinsed with water and dried; the dyeing obtained shows very good fastness to light, washing and milling.

EXAMPLE 3 To an ice-cold solution of 14.4 parts of 2-amino1-hydroxy-4-chlorobenzene, 17 parts of 30% hydrochloric acid and 100 parts of water is added a solution of 6.9 parts of sodium nitrite in 14 parts of water. The mixture is stirred at 0-5 until diazotization is complete, then after neutralization with sodium carbonate the diazo suspension is run into a solution at 0- 5" of 42 parts of 7 -hydroxynaphthyl-l-carbamic acid2-(4-methylphenyl-1-sulfonylarnino)-ethyl ester, 8.8 parts of sodium hydroxide and 10 parts of anhydrous sodium carbonate in 250 parts of water. When the coupling reaction is completed the dyestufi is isolated in the normal way.

28 parts of the sodium salt of the dyestuff so formed are heated at 80.with 400 parts of water and 30 parts of an 18% cobalt acetate solution (equivalent to 1.77 parts of cobalt). hydroxide solution is dropped in to give pH 9.5. When metallization is complete the cobaltiferous dyestufi is isolated and dried; it is a dark-colored powder which dyes wool and*polyamide' fibers in violet shades ofgoodallround fastnessi. r I I.

A very similar dyestutf is produced when instead of 42 parts -of 7-hydroxynaphthyl-1-carbamic acid-2-(4- methylphenyl-1"-sulfonylamino) -ethyl ester, 39- parts of 1 (4' methylphenyl; 1 sulfonylamino-acetylamino)- 7-hydroxynaphthalene are'employed. This latter-com pound is obtained by condensation of.-4..-methylphenyl1-- sulfonylamiuoacetic acid with 1-amino-7-hydroxynaphthalene or by heating at 80-90 for several hours 23.5 parts of .1chloroacetylamino 7-hydroxynaphthalene, 20

A sufficient amount of 10% sodium parts of 4-methylbenzene-1sulfonic acid amide and 6 parts of calcium oxide in 150 parts of water;

' EXAMPLE '4 15.4 parts or '2-arnino-1-hydroxy 4+nitrobenzene in a parts of waterat 5 are diazotized with a solution of 6.9 parts of sodium nitrite in 14 parts of water. The diazo suspension is carefully neutralized and run into" an ice-cold solution of 21 parts of 7-hydroxynaphthyl-1 carbamic acid-2-(4"-methyl-phenyl 1-"-sulfonlyamino) ethyl ester, 15.1 parts of l-(acetyl-aminoacetylamino)-7}- hydroxynaphthalene, 6.5 parts of sodium hydroxide and 10 parts of anhydrous sodium carbonate in 300 parts of Water. On completion of coupling the resultant dyestufi mixture is isolated in the usual manner and dried. The mixture is then dissolved in 300 parts of formamide, the solution heated to and 30 parts of crystallized chromic potassium sulfate gradually added in the course of 30 minutes. The mass is stirred at 100 until complex formation is complete. The dyestuif is precipitated by running in a dilute solution of common salt and is then filtered off and dried. The dark powder obtained on grinding dyes wool from neutral to weakly acid baths in olive shades which are fast to light, washing and milling. The dyestufi gives a very good reserve of cotton, polyacrylonitrile, polyester and acetate fibers when the material is cleared with hydrosulfite after dyeing. Silk dyeings can be almost completely stripped with hydrosulfite.

EXAMPLE 5 28.9 parts of 3-amino-4-hydroxyphenyl-l carbamic acid-72 (methylsulfonylamino)-ethyl ester in 200 parts of water and 25 parts of concentrated hydrochloric acid at 0-5 are diazotized with a solution of 6.9 parts of sodium nitrite in 14 parts of water. The diazonium compound is carefully neutralized with sodium carbonate and poured into an ice-cold solution of 16 parts of 2- hydroxynaphthalene, 8.8 parts of sodium hydroxide, 10 parts of anhydrous sodium carbonate and'250 parts of water. On completion of coupling the dyestuff is 'islolated in the normal way and dried to give a blueblack powder which, when dyed and afterchromed on wool yields blue shades of good fastness.

I EXAMPLE 6 When coupling is finished the dyestuff 'is'isolated' and 1 dried. The pulverized monoazo dyestufi is dissolvedin 400 parts of formamide, heated to 100-110 and 30 parts of crystallized chromic potassium sulfate are added to it in the course of '1 hour. The solution isrnain tained at 100-110 until formation of the complex is completed, it is then diluted with ample water and the chromiferous dyestuft precipitated by an' addition--of common salt, filtered oft, driedand ground. 'It isobtained as a dark powder which dissolves inlconcentrated sulfuric acid with 'a bluish red coloration and dyes wool.

from neutralor weakly acid baths in fastblue shades;

Very similar dyestuffs are obtained ,whenthe 29 parts of 6-hydroxynaphthyl-l-carbamic acid-T-(formylaminofethyl ester used-inthe, foregoing example is replaced by 26 parts of l-(formylaminoacetylamino)e6rhydroxy= naphthalene or by 30 parts of 6-hydroxynaphtliyl 1 carbamic acid-2-(acetylamino) -ethyl'ester.-- :9

EXAMPLE 7 p 26.2 parts of the dyestutr from diazotized ;2- hydroxy-4-chloro-S-nitrobenzene and ,7 hyd roxynaphthyl l-carbamic acid- 2':(inethylsulfonylamino) -ethyl '7 plus 21 parts of the dyestufi from diazotized Z-amino-lhydroxybenzene-4-sulfonic acid methylamide and 1- acetoacetylamino-2-methoxybenzene are dissolved in 350 parts of formamide. 15 parts of crystallized cobalt 2 liters of water and the chromium-containing dyestutf is precipitated with common salt. After subsequent filtering, drying and grinding a dark powder is obtained which gives bordeaux-red solutions in concentrated sulfuric acetate are added and the solution stirred at 100 until 6 acid and dyes wool, silk and synthetic polyamide fibers complete formation of the metal complex. The cobaltin fast black shades. containing dyestufi is isolated in the normal manner. It EXAMPLE dyes wool from neutral or weakly acid baths in green h 24.5 parts of the dyestufl. from diazotized 2-amino- EX 3 10 l-hydroxy-4-nitrobenzene and 6-hydroxynapthyl-1-carbarnic acid2-(methylsulfonylamino)-ethyl ester plus g g g gi g gz g fi gggggg gig' 17.3 parts of the dyestuff from diazotized 2-amino-l-hyhen g g l ester lus droxy-4-chloro-5-nitrobenzene and 2-hydroxynaphthalene 20 4 arts g esmff g' dmx 3 are converted into a chromium complex as described in p y y y Example 9 using 28 parts of crystallized chromic potaszene-4-sulfonic acid amide and 1-(3 -chlorophenyl)-3- o meth L5 razolone are dissolved in 400 arts of forma sium sulfate in formamide at 100-110 Isolated, dried y W p and ground, the chromium-containing dyestufi is a dark nude. 15 parts of crystallized cobalt acetate are added powder which dissolves in concentrated sulfuric acid and the solution stirred at 100 until the complex comwith a bordeaux-red coloration and dyes wool, silk and pound is completely formed. The cobalt-containing synthetic polyamide fibers in fast black shades. dyestutl is isolated in the noimal way, it dyes wool from In the followho tabl ar listed furthe d neutral to weakly acid baths in fast brown shades. 1 e r mqnoazo stutfs and metal-containing azo dyestufls which are ob- EXAMPLE 9 tainable according to the particulars of Examples 1, 2, 40 parts of the dyestulf produced from diazotized 2- 5 f 'nleY f characterized by the dial) and amino-1-hydroxy-4-nitrobenzene and 6-hydroxynaphthylcquplmg components, 111 Columns and the l-carbamic acid-2'-(4"-methylphenyl-l"-sulfonlyamino)- stltueflt R of t e (ham or coupling component or of ethyl ester plus 15.6 parts of the dyestuif obtained from f Components 111 column lthe form 111 Whlch P 2-amino-l-hydroxy-4-nitrobenzene and 7-hydroxynaph- P (Column (0) and the Shadfi 0f t e etalllzed thyl-l-carbamic acid-(2-dimethylaminosulfonylamino)- Y I O11 W001 (Column In c011111111 the ethyl ester are dissolved in 400 parts of formamide. The Substltuent R Stands for Y -y solution is heated to 100-110 and over the next hour group wherein x, alkylene and y have the meanings as- 28 parts of crystallized chromic potassium sulfate are signed to them in the appropriate columns. The abadded, the temperature of 100-110 being maintained breviations in column (IV) signify: Afterchr.=Afterthroughout until complete formation of the metal comchrome dyestufi, Cr-C=Chromium complex compound, plex compound. The reaction mass is then diluted with Co-C=Cobalt complex compound.

Table 1 Ex- R- NHCOz-alkylene-y Form in Shade of metal- No. Dlazo Component Coupling Component which llzed dyeing on applied wool alkylene z! 11.-. 2-amlno-1-hydroxy-4-R- z-hydroxynapththalene-fi- O ethylene phenylsulfonylemino.. afterchr.-- blue.

benzene. snlionic acid. 12 do 1-pheny1-3-methyl-5- O propionylamino Co--C. red-orange.

pyrazolone. 13--.- z-amino-l-hydroxy-fi 1-hydroxy-5chloro- O acetylamino (Ir-0--.- blue.

chloro-4-R-benzene. naphthalene. 14.--- 2-amino-1-hydroxy-4- l-acetoacetylamino-Q- O ethylureylene 00-0..-- reddish yellow.

methyl-fi-R-benzene. ethylhexane. 15.-.- 2-amino-1-hydroxy-4- 1-acetylamino-7-hydroxy- O butyrylamino Cr-C.- blue.

chloro-S-R-benzene. naphthalene.

l-(3-chloro)-pheny1-3- 0 acetylamino CrC- red.

methyl-5-pyrazolone. 17 do Z-hydroxynaphthalem-lifi- 0 do. afterchr-- blue.

disullonic acid. 18..-- 2-amino- -hydroxy-4-R- l-acetoaeetylamino- 0 .-.d0 do 00-0.--- reddish yellow.

benzene. benzene i-suli'onic acid morpholide. 19-..- 2-amiti1o-51B-beniZene-I- 2-hydroxynaphthalene 0 .do carbomethoxyamino" Cr-C.-- red-brown.

ear oxyic aci 20...- 2-amino-1-hydroxy-4-R- I-phenyl-3-methyl-5- 0 ....do 4-methylphenyl CrC red.

benzene. pyrazolone a sulfonie sullonylamino.

acit i(-i(2-hydroxy)-ethyl- 31111 e. 21--.. 2-aII1ino-5-R-henzene-1- l-aeetoaeetylamino-2- 0 -do formylamino (Jr-0--.. yellow.

carboxylic acid. methoxybenzene. 22 2-amino-1-hydroxy-4-nitro- 1-R6-hydroxynaphthalene 0 do n-butylsulfonyl- CrC black.

benzene. amino. 23. 2-amino-1-l'1ydroxydo 0 do acetylamino aiterehr-.- gray.

benzene-4-sullonic acid. 24 z-amino-l-hydroxy- 1-(4-R)-plieny1-3-rnethy1- 0 ...-do do (Jr-(L..- red.

benzene-4-sulfonic acid fi-py'razolone. methylaniide. 25 do 2-(4'-R)-phenyl-amino- 0 CrC- gray-violet.

naphthalene. 26. 2-amino-1-hydroxy-4 6- 1-R-7-hydroxynaphthalene- O atterchr.-. gray.

dichlorobenzene. 3-sulionic acid. 27 2-amino l-hydroxyi-nitrol-hydroxy-2-R4-methy1- 0 d0 methylsulfonyl- (Jr-0--.- brown.

benzene. benzene. amino. 28 do 1-R-6-hydroxynaphthalene 0 do do CrC black. 29 Z-aminobenzene-l-car- 1-acetoaeetylan1ino-3-R- 0 .d0 do CrG yellow.

boxylic acid. benzene. 30-. 2-amino-1-hydroxy-4-nitrol-hydroxy-Z-R--methyl- 0 do do 00-0..-- brown.

benzene. benzene. 31-... 2-amino-1-hydroxy-4-nitrol-Rbhydroxynaphthalenm. O diethylaminosul- (Jr-0--.. gray-black.

fichlorohenzene. fonylamlno. 32.... Z-aminobenzene-l-car- 1-(3'-R)-phenyl-3-mcthyl- O methylene 4-methylphenyl- Cr-C--. yellow.

boxylie acid E-pyrazolone. sulionylemino.

1-1 EXAMPLE 4 A mixture of the dyestufis:

12 EXAMPLE 7 A mixture of the dyestuifs:

II If Cr H+ EXAMPLE 6 A mixture of the dyestuffs:

7 EXAMPLES 2o 1 A mixture of the dyestuffs: C1 0 and 5 HN H CPOOC- -ILIH and r 1 I o,N- 0 o No,

w i i V NH-COO-CzHr-NH-SOGCH:

I PLEIO A mixture of the dyestuffs:

15 EXAMPLE 31 H Cr H+ N /NS 02-HN-H4Cr-O CNH a s 2 EXAMPLE 49 i CHa-SOrHN-HtCr-OOC-NH 1 Cr 11+ EXAMPLE 50 CIQOL l HN-HtOr-OOCNH N Cr 11+ I 301 l 0 H: 2

Having thus disclosed the invention what we claim is: I. A chromium complex dyestufl which corresponds to the formula I! Me 1E! N wherein s represents a member selected from the group consisting of chlorine, nitro and the sulfonic acid phenylamide p,

t represents a member selected from the group consisting of hydrogen and chlorine,

R represents a member selected from the group consisting of lower alkyl, mononuclear aryl and di-(lower alkyl)- amino,

X represents a bridge member selected from the group consisting of -SO;--- and CO, Me represents a heavy metal atom selected from the group consisting of Cr and Co,

and the group NHC0--O-C H NHSO R stands in one of the positions 5 and 8.

16 2. The chromium complex dyestutf which corresponds to the formula ll Cr 11+ CHs-SOr-HN-H4C2-O O C-ITTH N 3. The chromium complex dyestutf which corresponds to the formula HaG Cr H

4. The chromium complex dyestufi which corresponds to the formula CIQOL CH3 2 5. The chromium complex dyestufl which corresponds to the formula H Cr N C4Hr-S OPEN-HrCrO 0 C-NH 2 J 6. The chromium complex dyestuff which corresponds to the formula OIN- o 1 I ll F 01' H+ NSOz-HN-H|C:O 0 O-NH References Cited in the file of this patent FOREIGN PATENTS 312,963 Switzerland Apr. 30, 1956 407,055 Great Britain Mar. 9, 1934 785,345

Great Britain Oct. 23, 1957 l 

1. A CHROMIUM COMPLEX DYESTUFF WHICH CORRESPONDS TO THE FORMULA 